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WO2018158131A1 - Procédé de production de fluoroalkylnitriles et des fluoroalkyltétrazoles correspondants - Google Patents

Procédé de production de fluoroalkylnitriles et des fluoroalkyltétrazoles correspondants Download PDF

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Publication number
WO2018158131A1
WO2018158131A1 PCT/EP2018/054385 EP2018054385W WO2018158131A1 WO 2018158131 A1 WO2018158131 A1 WO 2018158131A1 EP 2018054385 W EP2018054385 W EP 2018054385W WO 2018158131 A1 WO2018158131 A1 WO 2018158131A1
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WIPO (PCT)
Prior art keywords
reactor
fluoroalkyl
general formula
nitriles
zeolite
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PCT/EP2018/054385
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German (de)
English (en)
Inventor
Albert Schnatterer
Jan Vermehren
Edith Beckmann
Claus Christian HÄSELHOFF
Tim HAMMERER
Stefan Grasser
Original Assignee
Bayer Cropscience Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Cropscience Aktiengesellschaft filed Critical Bayer Cropscience Aktiengesellschaft
Priority to DK18706515.6T priority Critical patent/DK3589612T3/da
Priority to US16/488,289 priority patent/US10899722B2/en
Priority to ES18706515T priority patent/ES2879861T3/es
Priority to CN201880014296.9A priority patent/CN110337428A/zh
Priority to EP18706515.6A priority patent/EP3589612B9/fr
Publication of WO2018158131A1 publication Critical patent/WO2018158131A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification

Definitions

  • the present invention relates to a process for the preparation of fluoroalkyl nitriles and the corresponding fluoroalkyl tetrazoles starting from fluorinated carboxylic acid amides.
  • Fluoroalkyl nitriles and the corresponding fluoroalkyl tetrazoles are important intermediates for the preparation of agrochemical active ingredients.
  • EP729940A2 reports the synthesis of fluorinated nitriles by reacting trifluoroacetic anhydride in a polar amide solvent such as e.g. DMF.
  • CN 103804231A (2014) discloses the preparation of trifluoroacetonitrile from the amide by the addition of trifluoroacetic anhydride in carbon tetrachloride.
  • US3274229A describes the dehydration of perfluorinated amides to the corresponding nitriles with the aid of Lewis acids, e.g. ZnCl.
  • CN 102746190A (2012) describes the preparation of trifluoroacetonitrile from the amide by the catalyst system polyphosphoric acid / phosphoric acid.
  • Kumar et al. (Chemistry and Industry, 1984, vol.7, 270, 1984) describes the dehydration of simple structured, thermally very stable carboxylic acid amides such as benzamide, phenylacetamide, nicotinamide and isopentanamide in the form of their vapors on ZSM-5 zeolites at 400 ° C with yields of 85-90%.
  • the publication does not describe the dehydration of fluoroalkylacetamides with zeolites.
  • Prasad et al. discloses the preparation of acetonitrile by acetamide dehydration over zeolites. Also in this publication, no fluoroalkylacetamides are used as starting materials.
  • Fernandez et al. reports the synthesis of acetonitrile by dehydration on active ZnO catalysts as compared to zeolite catalysts.
  • the publication does not describe the use of fluoroalkylacetamides as starting materials.
  • DE3600811A1 discloses the preparation of nitriles by catalytic dehydration of carboxylic acid amides on zeolitic catalysts in the presence of ammonia.
  • the publication does not describe the use of fluoroalkylacetamides as starting materials.
  • dehydrating reagents such as trifluoroacetic anhydride
  • dehydrating reagents such as trifluoroacetic anhydride
  • Recycling of the substances and solvents used is necessary.
  • phosphorus pentoxide this type of reaction usually results in no longer stirrable, solidified mixtures which preclude a large-scale implementation.
  • X 1 and X 2 independently of one another are a halogen, hydrogen or methyl, characterized in that fluorinated carboxamides of the formula (II)
  • X 1 and X 2 have the meanings given above, in the gas phase and in the presence of catalysts selected from the group of zeolites, aluminum phosphate, zirconium dioxide and heteropolyacids (preferably selected from the group of zeolites and aluminum phosphate and more preferably selected from Group of zeolites).
  • catalysts selected from the group of zeolites, aluminum phosphate, zirconium dioxide and heteropolyacids (preferably selected from the group of zeolites and aluminum phosphate and more preferably selected from Group of zeolites).
  • X 1 and X 2 independently of one another preferably represent fluorine, chlorine, hydrogen, methyl and more preferably only fluorine.
  • the fluoroalkyltetrazole of the formula (III) is preferably present in the form of the Na salt.
  • the fluorinated alkylamides of the formula (II) used according to the present invention are commercially available or can easily be prepared by processes known from the literature (WO 03/080563).
  • the fluorinated alkylnitriles of the formula (I) or fluoroalkyltetrazoles of the general formula (III) prepared therefrom can be classified under produce conditions of the invention safely and with good selectivities and yields in high purity.
  • the method according to the invention does not have the disadvantages described in connection with the prior art.
  • halogens or halides includes those elements selected from the group consisting of fluorine, chlorine, bromine and iodine, fluorine, chlorine and bromine being preferred and fluorine and chlorine being particularly preferred preferably used.
  • Optionally substituted groups may be monosubstituted or polysubstituted, with multiple substituents the substituents may be the same or different.
  • a reactor is charged with a catalyst (1.4 in Figure 1) described in this invention and optionally rendered inert with nitrogen. Thereafter, the desired reactor temperature is set (preferably between 200-500 ° C and more preferably between 250-350 ° C). Subsequently, the reaction gas (1.2 in Figure 1) fluorinated carboxylic acid of formula (II) (preferably in combination with an inert carrier gas such as nitrogen) switched.
  • the solid at room temperature fluorinated carboxylic acid of the formula (II) is preferably (in a heated piston pump) melted (1.1 in Figure 1) and fed via a heated line to an upstream evaporator (1.3 in Figure 1), in which it in the gaseous state is transferred.
  • the temperature in the evaporator is preferably between 200 and 300 ° C. If the fluorinated carboxylic acid amide of formula (II) is already liquid, it is fed directly to the evaporator via a pump. There is usually no limit to the amount of amide. From a technical point of view, a catalyst loading which causes neither too high a pressure loss nor too rapid catalyst deactivation nor an incomplete reaction. By-products or unreacted starting materials are condensed out by a condenser (1.5 in FIG. 1) at temperatures of preferably between 1 and 10 ° C.
  • Zeolites are crystalline aluminosilicates which can be found in numerous modifications in nature, but can also be prepared synthetically and, among others. can be used as catalysts.
  • Zeolites can be described by the following molecular formula:
  • M is typically a cation of an alkali or alkaline earth metal or an ammonium ion required for electrical charge balancing of the negatively charged aluminum-oxygen tetrahedra
  • n is the charge of the cation, which is typically 1 or 2
  • the molar ratio of S1O2 to AIO2 or y / x in the molecular formula is called the module, and the letter "z" indicates the number of water molecules absorbed by the crystal.
  • water is released from the crystal from about 250 ° C, so that z depends on the exact reaction conditions.
  • the molar ratio y / x has an influence on the number of Lewis acidic AI centers and on their relative strength among each other. It is variable in many areas. Preference is given to molar ratios of from 10 to 120, more preferably from 20 to 100.
  • Proton-form zeolites can also be prepared at the beginning of the process (quasi in situ) within the reactor.
  • all cations are suitable, which decompose at higher temperatures (> 150 ° C) in such a way that form a volatile component and a proton. Therefore, ammonium cations of the general form NHR3 + , which decompose into protons and NR3, are also preferred.
  • NR3R ' + organic ammonium cations of the form NR3R ' + , in which the organic radical R' decomposes by Hofmann elimination such that the radical R 'forms an olefin and protons.
  • a butyl radical can be cleaved by Hofmann elimination into a proton and a butene (preferably 1-butene).
  • the resulting NR3 should be as volatile as possible.
  • the zeolites which can be used have a structure which is selected from the structural types pentasil and MWW and very particularly preferably from the structure types MFI, MEL, mixed structures of MFI and MEL and MWW. More preferably, zeolites of the type ZSM-5 or MCM-22 are used.
  • the designations of the structure types of the zeolites correspond to the statements in WM Meier, DH Olson and Ch. Baerlocher "Atlas of Zeolite Structure Types", Elsevier, 3rd edition, Amsterdam 2001.
  • the synthesis of the zeolites is known to the skilled person and can, for example, starting from alkali aluminate , Alkali metal silicate and amorphous SiO 2 under hydrothermal conditions, whereby the type of channel systems formed in the zeolite can be controlled by means of organic template molecules, temperature and other experimental parameters.
  • the catalyst load is given at a constant catalyst mass (limited by the maximum possible pressure loss for the system). This is a reaction engineering Parameter indicating the mass flow or molar flow of educt with respect to the catalyst mass. Frequently, the volume of the catalyst bed is also used as a reference (see Gas Hourly Space Velocity or Weight Hourly Space Velocity). As a rule, the educt is diluted with an inert gas applied to the bed. This dilution is not specified.
  • a catalyst loading of 2 to 1000 mmol amide / (g * h), preferred from 3 to 700 and more preferably from 4 to 500 mmol amide / (g * h) is present.
  • the pressure loss is influenced by the shape of the catalyst particles.
  • Zeolites can be used as a powder. Often, however, the pressure loss is extremely high. In order to reduce the pressure loss of a zeolite powder bed, this powder bed may be packed with inert material, e.g. made of glass, as a shaped body a little looser. For use as a catalyst, the zeolites are therefore often used as a shaped body to keep the pressure loss of the bed low.
  • the catalyst is mixed with a binder. Suitable binders are the customary binders known to the person skilled in the art, such as aluminum oxide and / or Si-containing binders.
  • Si-containing binders In particular, tetraalkoxysilanes, polysiloxanes and colloidal SiC sols are suitable.
  • shaped zeolites is particularly preferred. All conceivable geometric shapes are possible, which lead to a loose packing of the bed. Particularly preferred are balls, cylinders and stars.
  • Zeolites are commonly used catalysts in the petroleum industry. They are used for isomerization or cracking of hydrocarbons. In addition, zeolites in different catalytic fields can act as a so-called carrier, to which then the actually catalytically active components (usually metals) are applied. Zeolites also serve for cleaning / drying (molecular sieves). Therefore, the zeolites are readily available commercially. Act as providers such as Clariant, BASF, Zeocem ®, Grace, Zeolyst, Zeo Inc., etc. ExxonMobil used many zeolites.
  • phosphorus is also involved.
  • phosphorus can be added to the zeolite.
  • the phosphorus may be added to the zeolite by any conventional means, such as mixing the Zeolites with an aqueous solution of a phosphorus compound such as a phosphate salt or phosphoric acid. Ammonium hydrogen phosphates are preferred sources of phosphorus.
  • aluminum phosphates or phosphorus-doped aluminum oxides are used as catalysts. Such materials can either be self-produced or are commercially available.
  • One possible supplier of aluminum phosphates is Clariant.
  • Aluminum phosphate can be obtained by reacting aluminum nitrate and ammonium phosphate in aqueous solution, specifically, mixing an aqueous solution of aluminum nitrate and an aqueous solution of ammonium phosphate prepared in a molar phosphorus aluminum ratio of 0.5 to 1.5, and this solution is now preferably adjusted at a pH of 7 to 9 by adding concentrated ammonium hydroxide solution. After drying the resulting hydrogel, this is heated to a temperature of over 500 ° Celsius (calcined).
  • the phosphorus-doped alumina is prepared by mixing alumina and phosphoric acid solution (impregnation). This solution typically contains from 0.1 to 30% by weight of phosphoric acid in the weight ratio of phosphoric acid to alumina.
  • the alumina has a specific surface area greater than 1 m 2 / g, preferably more than 10 m 2 / g. After removing the water, the product is heated at a temperature of over 500 ° C to fix the phosphorus on the alumina.
  • zirconium dioxide is used as the catalyst or catalyst component.
  • Zirconia is known as a ceramic material.
  • Zirconia has the ability to electrolytically conduct oxygen ions at higher temperatures. This property is used to measure different oxygen partial pressures, for example between exhaust gases and air (lambda sensor in the car).
  • Zirconia occurs in a variety of modifications that can transform into each other at higher temperatures: monoclinic (up to 1173 ° C) -> tetragonal (2370 ° C) -> cubic (2690 ° C).
  • the ceramics industry has been working hard to stabilize the phases by adding other oxides.
  • zirconium dioxides stabilized with other elements are commercially available. It is also known that zirconium dioxide can be converted into sulfated zirconia (see US-A 5 149 862), which is characterized by a higher acidity. Zirconia can be obtained, for example, from Saint-Gobain Norpro or Ceramtec. Also conceivable as catalysts are heteropolyacids (eg, tungstophosphoric acid).
  • compounds of the general formula (I) are present in a hot gas stream.
  • compounds inert to the gas stream such as e.g. Nitrogen, added.
  • the separation of the compounds of the general formula (I) is carried out by cooling in a cooling / cold trap. This may contain for support liquid or solid medium (solvent / activated carbon or the like) in which compounds of general formula (I) can be absorbed or adsorbed.
  • the isolation of the desired compounds of the general formula (I) from solvents can be carried out, for example, by distillation.
  • nitriles Another possibility for the functionalization of nitriles is the reaction with 1,3-dipolar compounds such as nitrile oxide, azide or diazoalkane. Frequently, such an implementation leads to heterocycles which play a role in the production of biologically active compounds. Thus, a nitrile reacts with an azide to form a so-called tetrazolate, i. Compounds of the general formula (III).
  • Particularly preferred according to the invention is the in situ generation of a nitrile of the formula (I) and the immediate reaction (without isolation) with an azide salt (preferably sodium azide) in a solvent to form the tetrazole compounds of the general formula (III).
  • an azide salt preferably sodium azide
  • the product-containing gas stream from the gas-phase dehydration described above is introduced via a scrubber (step 1.6 in FIG. 1) into a mixture (preferably into a stirred suspension) of sodium azide in a solvent (1.7 in FIG. 1).
  • an aprotic-polar solvent such as ketones such as acetone, lactones such as ⁇ -butyrolactone, lactams such as N-methyl-2-pyrrolidone, nitriles such as acetonitrile, Nitro compounds such as nitromethane, tertiary carboxylic acid amides such as dimethylformamide, urea derivatives such as tetramethylurea or dimethylpropyleneurea (DMPU), sulfoxides such as dimethyl sulfoxide (DMSO), sulfones such as sulfolane, carbonic acid esters such as dimethyl carbonate or ethylene carbonate used. Particular preference is given to using acetone or acetonitrile as solvent.
  • the scrubber (1.6 in FIG. 1) preferably contains a base for the removal of traces of acid in order to prevent the formation of explosive nitrogen-hydrogen-acid (possible formation by reaction of sodium azide with proton sources such as inorganic acids, carboxylic acids, alcohols, water). This is not only extremely reactive, but also reduces the amount of azide salt necessary for the intended reaction.
  • less nucleophilic bases such as pyridine or substituted pyridines and substituted or unsubstituted quinolines may be used.
  • Preferred examples of suitable bases are pyridine, picolines, quinoline, quinaldine and halogenated pyridines, and more preferably 3-picoline.
  • the sodium azide reactor (1.7 in FIG. 1) can be followed by, for example, two washing bottles of sodium hydroxide solution (20% strength) to further increase process reliability.
  • the reactor gas is then diluted so much that it can be supplied without endangering the exhaust air.
  • the process described above is preferably carried out continuously.
  • the flow rates are preferably chosen so that the respective residence time in the reactor in the range of 1.0 second to 1 minute, preferably from 1.0 sec. To 10 sec.
  • the pressure in the reactor is typically below 1 bar, preferably between 100 and 500 mbar and more preferably below 300 mbar.
  • the isolation of the desired compounds of the general formula (III) can be carried out, for example, by filtration.
  • the azide salt which is generally present in excess and is not always very soluble in the solvent, should have been previously separated off. Alternatively, it can be extracted with a slightly less polar, aprotic solvent.
  • the amount of sodium azide should be sufficient to allow complete reaction with the nitrile in a technically feasible time. If the excess of azide is too large, the salt, which can potentially decompose with release of nitrogen, must be separated again.
  • the molar ratio of azide / nitrile is preferably between 1 and 10, more preferably between 1 and 5 and particularly preferably between 1 and 2.
  • the amount of polar, aprotic solvent in which the azide salt is dissolved or suspended is not critical. Typical mixtures may contain up to 20% by weight of azide.
  • FIG. 2 Representation of the preparation of trifluoromethyltetrazolate sodium starting from trifluoroacetamide
  • TFMT-Na trifluoromethyl tetrazolate sodium
  • TFMT-Na trifluoromethyl tetrazolate sodium
  • the reactor is charged with 2.0 g zeolite HCZP 27E (Clariant) and rendered inert with nitrogen. After reaching the reaction temperature of 350 ° C, a nitrogen flow of 99 ml / min is set.
  • the average residence time in the reaction zone results from the reactor structure and is 2.9 sec.
  • the product gas stream is first passed through a cooled to + 4 ° C intensive cooler and then via a filled with 3-picoline scrubber in a suspension of 10 wt% sodium azide in acetone initiated.
  • TFMT-Na trifluoromethyl tetrazolate sodium
  • the reactor is filled with 5.0 g zeolite HCZP 55E (Clariant) and rendered inert with nitrogen. After reaching the reaction temperature of 400 ° C, a nitrogen flow of 99 ml / min is set.
  • the average residence time in the reaction zone results from the reactor structure and is 2.9 sec.
  • the product gas stream is first passed through a cooled to + 4 ° C intensive cooler and then via a filled with 3-picoline scrubber in a suspension of 10 wt% sodium azide in acetone initiated.
  • TFMT-Na trifluoromethyl tetrazolate sodium
  • TFMT-Na trifluoromethyl tetrazolate sodium
  • the product gas stream is first passed through a cooled to + 4 ° C intensive cooler and then via a filled with 3-picoline scrubber in a suspension of 10 wt% sodium azide in acetone initiated.
  • the resulting amount of trifluoromethyl tetrazolate sodium (TFMT-Na) in acetone is analyzed via 19 F NMR using an internal standard.
  • the yield of TFMT-Na based on the amount of trifluoroacetamide used is 4%.
  • TFMT-Na trifluoromethyl tetrazolate sodium
  • the product gas stream is first passed through a cooled to + 4 ° C intensive cooler and then via a filled with 3-picoline scrubber in a suspension of 10 wt% sodium azide in acetone initiated.
  • TFMT-Na trifluoromethyl tetrazolate sodium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pyridine Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

La présente invention concerne un procédé de production de fluoroalkylnitriles et des fluoroalkyltétrazoles correspondants à partir de carboxamides fluorés.
PCT/EP2018/054385 2017-02-28 2018-02-22 Procédé de production de fluoroalkylnitriles et des fluoroalkyltétrazoles correspondants WO2018158131A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DK18706515.6T DK3589612T3 (da) 2017-02-28 2018-02-22 Fremgangsmåde til fremstilling af fluoralkylnitriler og de tilsvarende fluoralkyltetrazoler
US16/488,289 US10899722B2 (en) 2017-02-28 2018-02-22 Process for the preparation of fluoroalkylnitriles and the corresponding fluoroalkyltetrazoles
ES18706515T ES2879861T3 (es) 2017-02-28 2018-02-22 Procedimiento para la fabricación de fluoronitrilos de alquilo y los correspondientes fluoronitrilos de alquilo
CN201880014296.9A CN110337428A (zh) 2017-02-28 2018-02-22 用于制备氟代烷基腈和相应的氟代烷基四唑的方法
EP18706515.6A EP3589612B9 (fr) 2017-02-28 2018-02-22 Procédés de préparation des nitriles fluoralkyles et des tétrazoles fluoralkyles correspondants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17158376.8 2017-02-28
EP17158376 2017-02-28

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WO2018158131A1 true WO2018158131A1 (fr) 2018-09-07

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US (1) US10899722B2 (fr)
EP (1) EP3589612B9 (fr)
CN (1) CN110337428A (fr)
DK (1) DK3589612T3 (fr)
ES (1) ES2879861T3 (fr)
TW (1) TW201843133A (fr)
WO (1) WO2018158131A1 (fr)

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CN109320436A (zh) * 2018-11-20 2019-02-12 北京宇极科技发展有限公司 气相催化制备全氟腈的方法

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CN114105820A (zh) * 2020-08-28 2022-03-01 浙江省化工研究院有限公司 一种七氟异丁腈的制备方法
CN114057605B (zh) * 2021-12-06 2024-02-20 化学与精细化工广东省实验室 气相脱水制备腈的方法

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CN109320436B (zh) * 2018-11-20 2021-03-23 北京宇极科技发展有限公司 气相催化制备全氟腈的方法

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